CN107039103A - Carbon nano tube compound material - Google Patents
Carbon nano tube compound material Download PDFInfo
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- CN107039103A CN107039103A CN201611036979.3A CN201611036979A CN107039103A CN 107039103 A CN107039103 A CN 107039103A CN 201611036979 A CN201611036979 A CN 201611036979A CN 107039103 A CN107039103 A CN 107039103A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/02—Single bars, rods, wires, or strips
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/81—Of specified metal or metal alloy composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/902—Specified use of nanostructure
- Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application
Abstract
The present invention provides a kind of carbon nano tube compound material.Carbon nano tube compound material (1) is included：Metal base (10), it is made up of the polycrystal for being oriented to equidirectional of multiple bar-shaped metal grains (11)；With carbon nanotube conducting path portion (20), it is made up of the doped carbon nanometer pipe with dopant, it is present in a part for the crystal boundary (15) between bar-shaped metal grain (11) in the cross section of metal base (10), and exist along the long side direction (L) of metal base (10), so as to be formed in the conductive conductive path of the long side direction of metal base (10).
Description
Technical field
The present invention relates to carbon nano tube compound material.
Background technology
In the prior art, as the method for the intensity for improving metal material, more and more uses are mixed in metal material
The method of 2nd metal different from the substrate metal (base metal) of metal material.But, if mixed in metal material
2nd metal, then the problem of electric conductivity that there is metal material declines to a great extent.
Therefore, carbon nano tube compound material just attracts attention.Because the intensity of CNT is high, and carry out electrical conductivity
(Japanese：バ リ ス テ ィ ッ Network Den Guide), compared with metal material, expect to improve intensity and electric conductivity.Currently it is proposed various carbon
Nanometer tube composite materials.
The composite wire rod with cell columnar structure is recorded in patent document 1, the cell columnar structure has：Comprising
The wall part of CNT；Covered and inside the next door that aluminum etc. is constituted with by wall part.In the composite wire rod, carbon
Nanotube is more than 0.2 weight %, below 5 weight % relative to the match ratio of aluminum.
The manufacture of composite wire rod described in patent document 1 is carried out as follows.I.e., first, to containing aluminium powder, carbon
The mixture of nanotube and elastomer is heat-treated, so that elastomer gasifies, obtains porous body.Secondly, porous body is made to exist
Plasma agglomeration is carried out in tank, blank is made.Further, extrusion molding is carried out to the blank, annealed at 500 DEG C,
So as to obtain composite wire rod.
Prior art literature
Patent document
Patent document 1：JP 2011-171291 publications
The content of the invention
Invent the technical problem to be solved
However, there is the problem of conductance is low such in the composite wire rod that patent document 1 is recorded.It is considered that its reason
It is that being formed with oxide scale film, resistance in the particle surface of aluminium powder raises, or the space in porous body, blank is in composite wood
Residual is hole in stockline material.
In addition, composite wire rod described in patent document 1 is low due to conductance, therefore CNT is relative to aluminium
The match ratio of material need mostly be more than 0.2 weight %, below 5 weight %, it is big, raw accordingly, there exist the use level of CNT
Produce the problem of cost is high such.
Also, in the composite wire rod described in patent document 1, CNT forms so-called cell columnar structure.
But, CNT is usually the mixture for containing semiconductor type carbon nano-tube and metal mold CNT, once semiconductor
Type CNT is contacted with metal mold CNT, then produces Schottky contacts.Composite wire rod described in patent document 1
It is formed with the cell columnar structure of the high CNT of the contact resistance because of Schottky contacts, therefore has that conductance is low such to ask
Topic.
In addition, for the composite wire rod described in patent document 1, in aluminium powder and CNT Composite, carbon
Nanotube bends, deformed, so that the problem of conductance that there is CNT declines such.
Although being recorded it should be noted that having in patent document 1 using the CNT after adulterating is such, to mixing
The effect of CNT after miscellaneous, using CNT after doping the reasons why, recorded without any.
The present invention be in view of above-mentioned item and complete, the purpose is to provide, conductance is high and use level of CNT is few
Carbon nano tube compound material.
Technological means for solving problem
The carbon nano tube compound material that is related to of a technical scheme of the present invention is characterised by, including：Metal base, its
It is made up of polycrystal, multiple bar-shaped metal grains is oriented to equidirectional in the polycrystal；And carbon nanotube conducting road
Footpath portion, it is made up of the doped carbon nanometer pipe with dopant, is present in the cross section of the metal base described bar-shaped
A part for crystal boundary between metal grain, and exist along the long side direction of the metal base, so as to be formed in the gold
Belong to the conductive conductive path of the long side direction of base material.
Can also be that dopant is constituted from by the material containing halogens, the material of alkali metal containing and metal oxide
Group in more than one dopants for selecting.
Can also be that the material containing halogens is more than one yuan selected from the group being made up of fluorine, chlorine, bromine and iodine
Element, the ion comprising more than one elements, the molecule comprising more than one elements or its compound.
Can also be that the material of alkali metal containing is more than one that selected from the group being made up of lithium, sodium, potassium, rubidium and caesium
Element, the ion comprising more than one elements, the molecule comprising more than one elements or its compound.
Can also be that metal oxide is from by iron oxide, cupric oxide, titanium oxide, zinc oxide, molybdenum oxide and calcium oxide group
Into group in more than one oxides for selecting.
Can also constitute the dopant of doped carbon nanometer pipe relative to the mass parts of CNT 100, have 0.04~
1.6 mass parts.
Can also constitute the dopant attachment of doped carbon nanometer pipe or be contained in CNT.
Can also, relative to the mass parts of metal base 100, contain the mass of carbon nanotube conducting path portion 0.1~1
Part.
Invention effect
The conductance height for the carbon nano tube compound material that the technical scheme of the present invention is related to and the cooperation of CNT
Amount is few.
Brief description of the drawings
Fig. 1 is the stereogram for the part for showing carbon nano tube compound material of the present embodiment.
Fig. 2 is the sectional view for schematically showing the section along Fig. 1 line A-A.
Fig. 3 is the sectional view for schematically showing the section along Fig. 1 line B-B.
Fig. 4 is the figure of one of the doping treatment for showing CNT.
Fig. 5 is the figure of one of the Raman spectrum for showing the CNT before and after doping treatment.
Fig. 6 is that the transmission electron microscope (TEM) of carbon nano tube compound material longitudinal section of the present embodiment shines
One of piece.
Fig. 7 is that the transmission electron microscope (TEM) of carbon nano tube compound material longitudinal section of the present embodiment shines
Another example of piece.
Fig. 8 is the figure of one for showing powder compact forming process.
Fig. 9 is the figure illustrated to the scope that the pressure of mixed-powder is applied in powder compact forming process.
Figure 10 is the figure of one for showing to extrude manufacturing procedure.
Figure 11 is the pass for showing the relative electric conductivity of the doping of iodine and carbon nano tube compound material in doped carbon nanometer pipe
The chart of system.
Embodiment
[carbon nano tube compound material]
Hereinafter, referring to the drawings, the carbon nano tube compound material of present embodiment is illustrated.
Fig. 1 is the stereogram for the part for showing carbon nano tube compound material of the present embodiment.Need explanation
It is that carbon nano tube compound material 1 is that the edge in carbon nano tube compound material 1 is only shown in the wire rod extended along long side direction, Fig. 1
A part behind long side direction L cut-outs two ends.Fig. 2 is the sectional view for schematically showing the section along Fig. 1 line A-A.Fig. 3 is
Schematically show the sectional view of the section along Fig. 1 line B-B.
As shown in Figures 2 and 3, the carbon nano tube compound material 1 of present embodiment possesses：Metal base 10 and CNT are led
Power path portion 20.
(metal base)
Metal base 10 is made up of polycrystal, in the polycrystal, and the orientation of multiple bar-shaped metal grains 11 is equidirectional.
Bar-shaped metal grain 11 is constituted such as the metal by aluminium, aluminium alloy, copper, copper alloy.The metal of these metal grains
Electric conductivity it is high, therefore preferably.It should be noted that bar-shaped metal grain 11 can also contain inevitable impurity.It is bar-shaped
The concentration of inevitable impurity in metal grain 11 is below 10 mass %.
In an embodiment of the invention, bar-shaped metal grain 11 be meant that the ratio of width to height for more than 1 it is bar-shaped
Metal grain.The ratio of width to height is defined as long side (length of the long side direction of bar-shaped metal grain) and the short side (rod of metal grain
The length of the cross direction of shape metal grain) ratio.The ratio of width to height can be determined by scanning electron microscope (SEM).
The cross sectional shape of bar-shaped metal grain 11 does not have specific restriction.It should be noted that in fig. 2, although show rod
The section shape of shape metal grain 11 is hexagon, but it can also be beyond hexagon to be bar-like the section shape of metal grain 11
Shape.
The length of bar-shaped metal grain 11 is, for example, 0.1~200 μm.Herein, the meaning of the length of bar-shaped metal grain 11
Refer to the length of the long side direction of bar-shaped metal grain.In addition, the equivalent diameter of the crystal grain of bar-shaped metal grain 11
(diameter-equivalent) it is, for example, 0.1~100 μm.Herein, the equivalent diameter of the crystal grain of bar-shaped metal grain 11 refers to
Average crystalline diameter in the cross section of bar-shaped metal grain 11.The length and equivalent diameter of bar-shaped metal grain 11 are in above-mentioned model
In enclosing, also, it is thinner, the intensity of metal base 10 is higher.
Metal base 10 is polycrystal, wherein, multiple crystal grain of these bar-shaped metal grains 11 are oriented to equidirectional,
And adjacent bar-shaped metal grain 11 is combined in grain boundaries each other.Herein, the orientation of multiple crystal grain of bar-shaped metal grain 11
For being meant that for equidirectional, the long side direction of bar-shaped metal grain 11 is towards equidirectional.
It should be noted that the carbon nano tube compound material 1 of present embodiment is by the long side side shown in Fig. 1 and 3
Extrusion processing is carried out to L and is manufactured.In figure 3, multiple bar-shaped metal grains 11 are oriented to and long side direction L phase Tongfangs
To.
So, the reasons why orientation of multiple bar-shaped metal grains 11 is with long side direction L equidirectionals is to be not arranged in spy
Equidirectional can be drawn as by extruding processing during fabrication by determining the metal grain in direction.
It should be noted that the carbon nano tube compound material 1 of present embodiment is extruded processing and manufactured, but this
The carbon nano tube compound material of invention can also be manufactured with the method beyond extrusion processing.
(carbon nanotube conducting path portion)
As shown in Figures 2 and 3, in carbon nano tube compound material 1, at one of the mutual crystal boundary 15 of bar-shaped metal grain 11
Point, it there are carbon nanotube conducting path portion 20.Multiple carbon nanotube conducting path portions are formed in carbon nano tube compound material 1
20。
Carbon nanotube conducting path portion 20 is made up of the doped carbon nanometer pipe with dopant, is formed in metal base 10
The conductive conductive path of long side direction.
＜ doped carbon nanometer pipes ＞
The doped carbon nanometer pipe for constituting carbon nanotube conducting path portion 20 is the CNT with dopant.For doping
CNT, the form as CNT with dopant can enumerate dopant and be attached to or be contained in CNT
Form.Doped carbon nanometer pipe is, for example, by making to adhere to or comprising obtained from dopant in known CNT.
[CNT]
Can be that multilayer carbon nanotube, monolayer carbon are received as the Rotating fields of the CNT of the raw material of doped carbon nanometer pipe
Mitron etc., is not particularly limited.Wherein, multilayer carbon nanotube easily adheres to or is contained in CNT due to dopant, therefore
It is preferred that.
[dopant]
Constitute doped carbon nanometer pipe dopant refer in CNT attachment or comprising material, also, be to improve
The material of the conductance of doped carbon nanometer pipe.In the present embodiment, the dopant for constituting doped carbon nanometer pipe is from by halogen
More than one dopants selected in the group of the material of prime element, the material of alkali metal containing and metal oxide composition.In addition,
Dopant is selected from the group being made up of the material containing halogens, the material of alkali metal containing and metal oxide except above-mentioned
Outside more than one dopants, also it can also contain from by acid, oxidant, electroconductive polymer, ionic liquid and organic molecule
More than one dopants selected in the group of composition.
For the material containing halogens as dopant, it is, for example, possible to use from being made up of fluorine, chlorine, bromine and iodine
More than one elements, the ion comprising more than one elements, the molecule for including more than one elements selected in group
Or its compound.Herein, ion refers to the concept comprising monatomic ion and multi-atomic ion.In addition, the meaning of " its compound "
Think of refers to, the polynary system material comprising more than one described elements He other race's elements.In the above-mentioned material containing halogens, iodine
CNT is easily attached to or is contained in, therefore preferably.Iodine to CNT adhere to or comprising when, for example, using I-、
I3-、I5-Etc. form.As the above-mentioned material containing halogens, for example using sodium iodide (NaI), cupric iodide (CuI), FeI,
FeCl3、MoCl3、CuCl2And AuCl3。
For the material of the alkali metal containing as dopant, such as using from the group being made up of lithium, sodium, potassium, rubidium and caesium
More than one elements for selecting, the ion comprising more than one elements, the molecule comprising more than one elements or its
Compound.Therefore alkali metal, for CNT, play a role because electronegativity is small, easy ejected electron as alms giver.
Be responsible in material conductive carrier exist electronics and hole both.Wherein, the principal carrier of metal material is usually electricity
Son.On the other hand, the principal carrier of CNT is known as absorption of the oxygen in air etc. and turns into hole.If main
Contacted between the different foreign material of carrier, then form the potential barriers such as Schottky barrier.Therefore, if metal material and carbon nanometer
(CNT) contact is managed, then the carrier movement between metal-CNT is obstructed, and conductance is possible to decline.In this case, such as
Fruit uses the material of the alkali metal containing for containing alkali metal as dopant, then the principal carrier of CNT and metal is main
Carrier similarly turns into electronics, the decline for the conductance that can suppress the formation with potential barrier and bring.Therefore, if used
Contain the material of alkali metal containing of alkali metal as dopant, then the conductance of carbon nano tube compound material is easily uprised.It is above-mentioned
In alkali metal, potassium easily adheres to or is contained in CNT, and electronegativity is small, therefore preferably.
For the metal oxide as dopant, for example, it can use from by iron oxide, cupric oxide, titanium oxide, oxidation
More than one oxides selected in the group of zinc, molybdenum oxide and calcium oxide composition.As iron oxide, such as using Fe2O3、
Fe3O4.As cupric oxide, such as using CuO, CuO2.As titanium oxide, such as using TiO2.As zinc oxide, for example, use
ZnO.As molybdenum oxide, such as using MoO2、MoO3.In above-mentioned metal oxide, MoO3Easily adhere to or be contained in carbon nanometer
Pipe, therefore preferably.Metal oxide is compared with CNT, and work function is big, therefore generates multiple current-carrying by 1 metal oxide
Son, and be entrained in CNT.Therefore, if using metal oxide as dopant, making the doping of identical quantity
In the case that agent is adhered to or is contained in CNT, higher doping effect can be obtained.
For the acid as dopant, for example, it can use from by sulfuric acid, nitric acid, hydrochloric acid, PF6、AsF5、BBr2And SO3Group
Into group in select more than one acid or its ion.For the oxidant as dopant, for example, it can use from by peroxide
More than one compounds selected in the group for changing hydrogen and potassium permanganate composition or its ion.The knot such as defect of acid and CNT
Close.Therefore, in the case where using acid as dopant, carrier can be moved directly between acid and CNT, therefore
Higher doping effect can be obtained.In above-mentioned acid, the oxidability of nitric acid is strong, is easily combined with CNT.Therefore, if
Using nitric acid as dopant, then higher doping effect can be obtained.
As described above, as long as dopant is from the material and metal oxide by the material containing halogens, alkali metal containing
More than one the dopant selected in the group of composition, therefore, it is possible to and use dopant.For example, as dopant, can
And with iodine and sodium or and with iodide ion and sodium ion.
Relative to the mass parts of CNT 100, generally there is 0.04~1.6 mass in the dopant for constituting doped carbon nanometer pipe
Part, preferably 0.044~1.5 mass parts, more preferably 0.044~1.2 mass parts.If the adhesion amount or content of dopant are upper
In the range of stating, then compared with using the situation of the CNT without dopant, the facing conductive of carbon nano tube compound material
Rate is uprised.
It should be noted that having used the carbon nano tube compound material of doped carbon nanometer pipe and having used without dopant
The carbon nano tube compound material of CNT compare, the reasons why conductance is uprised can be speculated as follows.
Generally, the conductance of material is proportional to carrier density.If result, it is believed that adhering to CNT
Or comprising dopant, then compared with the CNT without dopant, the carrier density in doped carbon nanometer pipe is improved, from
And conductance is uprised.Therefore, the carbon nano tube compound material of doped carbon nanometer pipe has been used and has used without dopant
The carbon nano tube compound material of CNT is compared, and the carrier density in carbon nano tube compound material is improved, so that conductance
Uprise.
In addition, CNT is usually the mixture for containing semiconductor type carbon nano-tube and metal mold CNT.So
And, if semiconductor type carbon nano-tube and the contact of metal mold CNT, occur Schottky contacts, therefore contact resistance becomes
It is high.Therefore, as the CNT for the carbon nanotube conducting path portion 20 for constituting carbon nano tube compound material 1, if semiconductor
Type CNT is contacted with metal mold CNT, then as Schottky contacts, therefore contact resistance is uprised, and CNT is led
Electric rate step-down.If in this regard, it is believed that making CNT attachment or comprising dopant, received with the carbon without dopant
Mitron is compared, the Schottky contacts resistance reduction between CNT, so that conductance is uprised.Therefore, doped carbon nanometer has been used
The carbon nano tube compound material of pipe is compared with having used the carbon nano tube compound material for the CNT for not having dopant, and carbon is received
Schottky contacts resistance reduction in mitron composite, so that conductance is uprised.
As set forth above, it is possible to think, in doped carbon nanometer pipe, with dopant, so as to produce carrying for carrier density
Height effect and the reduction of Schottky contacts resistance are acted on, and the conductance in carbon nano tube compound material is uprised.Therefore, generally, it is excellent
Select the dopant dose in doped carbon nanometer pipe more.Specifically, preferably as described above, relative to the mass of CNT 100
Part, dopant exists with amounts more than 0.04 mass parts.
It should be noted that if the dopant dose of doped carbon nanometer pipe were excessive, the carrier in doped carbon nanometer pipe
Mean free path it is too short, produce conductance reduction it is such the problem of.Therefore, the dopant dose of doped carbon nanometer pipe is not preferably
Excessively.Specifically, preferably as described above, relative to the mass parts of CNT 100, dopant with 1.6 mass parts below
Amount is present.
The diameter of doped carbon nanometer pipe is, for example, 0.4~50nm.The average length of CNT is, for example, more than 1 μm.
[manufacture method of doped carbon nanometer pipe]
Doped carbon nanometer pipe for example can be by making CNT adhere to or be manufactured comprising dopant.As to carbon nanometer
The method that pipe adheres to or makes it include dopant, for example, can use electrolysis, vacuum vapour deposition, steam exposure method, solution leaching
Stain method, spraying process etc..
Electrolysis refers to following methods：In the electrolyte containing dopant ion, make CNT dipping wherein
Or in the state of being in contact with it, produce potential difference between CNT and the opposing party's electrode, make the dopant in electrolyte attached
Or be contained in CNT.
Electrolysis is for example carried out using the electrolysis unit 30 shown in Fig. 4.Electrolysis unit 30 has：Electrolytic cell 31, its energy
It is enough to accumulate the electrolyte 35 for including the dopants such as iodide ion；The Pt anodes 33 of tabular, it can load CNT 40；It is cloudy with Pt
Pole 34, it can be electrolysed between Pt anodes 33.
For example, in the electrolytic cell 31 of electrolysis unit 30, filling electrolyte 35, CNT is loaded on Pt anodes 33
40, it is electrolysed between Pt negative electrodes 34 and Pt anodes 33, so that the dopant obtained in electrolyte 35 is attached to or is contained in
The doped carbon nanometer pipe of CNT.CNT adheres to or included dopant for example can as illustrated in fig. 5, by determining
The Raman spectrum of CNT before and after electrolysis processing (doping), so as to be confirmed.
Vacuum vapour deposition refers to CNT vacuum evaporation dopant, CNT is adhered to or the side comprising dopant
Method.Steam exposure method refers to CNT in the steam of dopant, CNT is adhered to or comprising dopant
Method.Solution dipping method refers to impregnate CNT in the solution containing dopant, CNT is adhered to or comprising doping
The method of agent.Spraying process refers to CNT spray dosing agent, CNT is adhered to or the method comprising dopant.
It should be noted that the form of attachment or the CNT comprising dopant is not particularly limited, for example, it can set
It is set to powdered, fibrous, paper-like.As the CNT of paper-like, such as using known Buckie paper.If making the carbon of paper-like
Nanotube adheres to or comprising dopant, then generally yields the doped carbon nanometer pipe of paper-like.On the other hand, the carbon of present embodiment is received
The form of the doped carbon nanometer pipe used in mitron composite is typically powdered.Therefore, the doped carbon nanometer pipe example of paper-like
Apply ultrasonic activation etc. in a solvent as impregnated, dissolved, remove solvent, so that as powdered.
The shape ＞ of doped carbon nanometer pipe in ＜ carbon nanotube conducting path portions
Carbon nanotube conducting path portion 20 includes more than 1 doped carbon nanometer pipe.Constitute carbon nanotube conducting path portion 20
Doped carbon nanometer pipe can be that 1 or more than 2 doped carbon nanometer pipes exist with extension state, bulk can also be aggregated into.
As shown in Fig. 2 being present in bar-shaped metal grain in the cross section of the metal base 10 of carbon nanotube conducting path portion 20
A part for crystal boundary 15 between 11.That is, in the cross section of metal base 10, carbon nanotube conducting path portion 20 is not to exist
In the whole crystal boundary 15 of bar-shaped metal grain 11.Therefore, carbon nanotube conducting path portion 20 is without the bar-shaped metal grain of covering
Construction around 11.In addition, as shown in Fig. 2 carbon nanotube conducting path portion 20 exist it is multiple in the case of, generally, carbon
Nanotube conductive path portion 20 exists apart from each other.
It should be noted that being used as existing carbon nano tube compound material, it is known that carbon nanotube conducting path portion covers rod
The carbon nano tube compound material of the so-called cell columnar structure of the whole surrounding of shape metal grain.The cell columnar structure is in carbon nanometer
The construction of bar-shaped metal grain is incorporated with the cell that pipe conductive path portion is formed.Cell columnar structure generally comprises multiple thin
Born of the same parents, and as the honeycombed structure linked in the way of the shared wall of adjacent 2 cells.In the cell columnar structure,
It is present in the construction of the whole crystal boundary between bar-shaped metal grain as carbon nanotube conducting path portion.
On the other hand, in carbon nano tube compound material 1 of the present embodiment, in the cross section of metal base 10
In, a part for the crystal boundary 15 that carbon nanotube conducting path portion 20 is existed only between bar-shaped metal grain 11 is not present in whole
Crystal boundary 15.Therefore, carbon nano tube compound material 1 of the present embodiment will not form carbon nanotube conducting path portion 20 and cover
The cell of bar-shaped metal grain 11, is constructed significantly different with cell columnar structure.
As shown in figure 3, long side direction L of the carbon nanotube conducting path portion 20 along metal base 10 is present, so as to be formed
In the conductive conductive path of the long side direction of metal base 10.It should be noted that in carbon nano tube compound material 1, carbon is received
Long side direction L of the mitron conductive path portion 20 along metal base 10, by it is continuous, interrupted or both in the way of exist.
For example, in figure 3,3 carbon nanotube conducting path portion 20a, 20b and 20c are continuously deposited along long side direction L
.Herein, what is be continuously present is meant that, is in contact with each other in the adjacent carbon nanotube conducting path portions 20 of long side direction L.
In addition, in figure 3,3 carbon nanotube conducting path portion 20d, 20e and 20f are intermittently deposited along long side direction L
.Herein, what is intermittently existed is meant that, is not contacted each other in the adjacent carbon nanotube conducting path portions 20 of long side direction L.
It should be noted that for carbon nanotube conducting path portion 20, at least a portion carbon nanotube conducting path portion 20
Exist along the long side direction L of metal base 10.It therefore, there is no need to all carbon nanotube conducting path portions 20 along gold
The long side direction L for belonging to base material 10 is present.For example, in carbon nano tube compound material 1 of the present embodiment or one
The differently- oriented directivity of part carbon nanotube conducting path portion 20 is not along the long side direction L of metal base 10.Now, CNT is multiple
The differently- oriented directivity of carbon nanotube conducting path portion 20 in condensation material 1 is unordered.
So, it is not necessarily multiple carbon nanotube conducting paths in carbon nano tube compound material 1 of the present embodiment
Long side direction L of the portion 20 along metal base 10 is continuously present.But, because metal base 10 itself is conductive, because
This, even if carbon nanotube conducting path portion 20 is separated from each other, can also turn on via metal base 10.
In figure 6 and figure 7, the use FIB (focused ions of carbon nano tube compound material obtained in aftermentioned embodiment 1 are shown
Beam method) processing after longitudinal section transmission electron microscope (TEM) photo.Herein, longitudinal section refers to multiple along CNT
The long side direction L of condensation material section.Fig. 6 and Fig. 7 are the photos observed with the different visuals field in same material longitudinal section.Need
Illustrate, in figure 6 and figure 7, the region present in carbon nanotube conducting path portion 20 is represented with label C.Can by Fig. 6
Know, carbon nanotube conducting path portion 20 intermittently exists between bar-shaped metal grain 11 along long side direction L.In addition, can by Fig. 7
Know, carbon nanotube conducting path portion 20 is between bar-shaped metal grain 11 along long side direction L and perpendicular direction (in Fig. 7
Lower section) exist deviously.
In carbon nano tube compound material 1 of the present embodiment, relative to 100 mass parts metal bases 10, carbon is received
Mitron conductive path portion 20 usually contains 0.1~1 mass parts, preferably comprises 0.2~1 mass parts, further preferably 0.5~1 matter
Measure part.It should be noted that 100 mass parts metal bases 10 are meant that, 100 mass parts phases with bar-shaped metal grain 11
Together.
If the content of carbon nanotube conducting path portion 20 is within the above range, carbon nanotube conducting path portion 20 is easy
It is present in a part for the crystal boundary 15 between bar-shaped metal grain 11 in the cross section of metal base 10.
It should be noted that in the carbon nano tube compound material of existing cell columnar structure, carbon nanotube conducting path
Portion forms the wall of cell.Therefore, in the carbon nano tube compound material of existing cell columnar structure, carbon nanotube conducting path portion
Content substantially more to 1~5 mass parts degree.
On the other hand, carbon nano tube compound material 1 of the present embodiment is not cell columnar structure, carbon nanotube conducting
Path portion 20 is present in a part for the crystal boundary 15 between the bar-shaped metal grain 11 in the cross section of metal base 10.Cause
This, in carbon nano tube compound material 1 of the present embodiment, the content of carbon nanotube conducting path portion 20 can be with less.
The conductance of carbon nano tube compound material 1 of the present embodiment is high, and the use level of CNT is few.Need
Illustrate, the reasons why conductance of carbon nano tube compound material 1 is uprised be considered as, first, carbon nano tube compound material 1 is not
With cell columnar structure, therefore, elastomer need not be used during manufacture, in the absence of the gasification because of elastomer caused by residue.
In addition, the conductance of carbon nano tube compound material 1 is considered as the reasons why uprising, second, carbon nanotube conducting path portion 20 by
Doped carbon nanometer pipe with dopant is constituted, therefore, produces raising effect and the Schottky contacts resistance of carrier density
Reduction is acted on.
[manufacture method of carbon nano tube compound material]
Then, referring to the drawings, the manufacture method for the carbon nano tube compound material being related to embodiment is illustrated.
The manufacture method of the carbon nano tube compound material of present embodiment has doped carbon nanometer pipe production process, powder pressure
Base forming process and extrusion manufacturing procedure.
(doped carbon nanometer pipe production process)
Doped carbon nanometer pipe production process is the process for making CNT adhere to or include the iodine as dopant.Doped carbon
Nanotube production process is the manufacture method identical process with above-mentioned doped carbon nanometer pipe.Therefore, the explanation of this process is omitted.
(powder compact forming process)
Powder compact forming process is to apply pressure, shaping to the mixed-powder comprising metal dust and doped carbon nanometer pipe
The process of the powder compact of powder.
＜ metal dusts ＞
As metal dust, such as using aluminium powder, Al alloy powder, copper powders, copper alloy powder.These metal dusts
Electric conductivity it is high, therefore preferably.The average grain diameter D of metal dust50E.g. 1~500 μm, preferably 3~300 μm.Herein,
D50Indicate median particle diameter.If the average grain diameter D of metal dust50Within the above range, then it is readily obtained the carbon of present embodiment
Nanometer tube composite materials 1.In addition, metal dust can also be average grain diameter D50The mixture of different various metals powder.Such as
Fruit metal dust is average grain diameter D50The mixture of different various metals powder, then the gap between metal powder particles diminish,
Therefore it is easily formed the powder compact of powder.
＜ doped carbon nanometer pipes ＞
As doped carbon nanometer pipe, doped carbon nanometer used in the carbon nano tube compound material with present embodiment is used
Pipe identical doped carbon nanometer pipe.It should be noted that it can also be in attachment that the raw material of doped carbon nanometer pipe, which is CNT,
Or comprising dopant before, cleaned with acid, so as to eliminate the metallic catalysts such as platinum, amorphous carbon, or pre- advanced
Row high-temperature process, so that amorphous carbon graphitization., can be to obtaining if carry out such pre-treatment to CNT
Doped carbon nanometer pipe carries out high purity, highly crystallineization.For item in addition, answered with the CNT of present embodiment
What is illustrated in condensation material is identical, therefore omits the explanation to doped carbon nanometer pipe.
＜ mixed-powders ＞
Mixed-powder is the powder containing metal dust and doped carbon nanometer pipe.Mixed-powder is, for example, by by metal powder
End and doped carbon nanometer pipe are mixed in alcohol series solvent equal solvent, and the method for making solvent gasify is obtained.
Relative to the mass parts of metal dust 100, mixed-powder usually contains the mass parts of doped carbon nanometer pipe 0.1~1, preferably
Be 0.2~1 mass parts, more preferably 0.25~1 mass parts.
In powder compact forming process, apply pressure to above-mentioned mixed-powder to compress, so that the powder of formed powder
Pressed compact.In powder compact forming process, mixed-powder is compacted so that the gap between metal powder particles in mixed-powder
Reach minimum.As stressed method is applied to mixed-powder, known method can be used, for example, using by mixed powder
After end is put into the powder compact forming containers of tubular, to the method for the mixed-powder pressurization in the container.
In the powder compact of obtained powder, doped carbon nanometer pipe is typically found between the metal powder particles being compacted
Gap.Doped carbon nanometer pipe can exist with the state of 1 or more than 2 doped carbon nanometer pipe extension, simply by the presence of in gold
Belong to powder particle between gap, can also aggegation and as bulk.
Referring to the drawings, powder compact forming process is illustrated.Fig. 8 is show powder compact forming process one
Figure.The powder compact forming containers 80 shown in Fig. 8 are for applying pressure to mixed-powder 50 with the powder pressure of formed powder
The container of base 60.Powder compact forming containers 80 include the container body 81 of tubular, and the container body 81 is provided with and passed through in direction of principal axis
Logical columned blank part 83.
In powder compact forming process, first, powder compact forming containers 80 are positioned on bottom plate (not shown).This
When, powder compact forming containers 80 between the bottom surface of powder compact forming containers 80 and the surface of bottom plate by not produce gap
Mode load.Next, putting into mixing into the blank part 83 for the powder compact forming containers 80 that bottom side is clogged with bottom plate
Powder 50.Further, pressure is applied to the mixed-powder 50 in blank part 83 with reference F1 power, to compress mixed-powder
50, so that the powder compact 60 of formed powder.
The pressure for being applied to mixed-powder 50 in powder compact forming process using reference F1 power is set to
More than the yield stress of the metal dust in mixed-powder 50, below maximum stress.For example, the metal powder in mixed-powder 50
In the case that end is aluminium powder, pressure is applied to mixed-powder 50 so that the pressure for it is more than the yield stress of aluminium powder, it is maximum
Pressure below stress.If being applied to the surrender for the metal dust that the pressure of mixed-powder 50 is set as in mixed-powder 50
More than stress, below maximum stress, then shape and compressed in the way of the mutual gap of the metal dust in mixed-powder 50 is minimum
The powder compact 60 of the powder of mixed-powder 50.
Herein, the stress being meant that at the boundary point of elastic deformation and plastic deformation of yield stress.That is, metal powder
The metal materials such as end are generally in the small region of dependent variable, relative to the increase of dependent variable, and also proportionally increase is (elastic for stress
Deformation), but if it exceeds predetermined dependent variable, then relative to the increase of dependent variable, stress no longer proportionally increases (plasticity
Deformation).Stress under the predetermined dependent variable is referred to as yield stress.In addition, maximum stress refers to, in elastic deformation and plasticity
Deform the maximum of the stress in the two regions.The maximum stress of metal material is typically found in plastic deformation area.
The pressure for being described with reference to be applied to mixed-powder 50 is more than the yield stress of metal dust, maximum stress with
Under pressure.Fig. 9 is the figure illustrated to the scope that the pressure of mixed-powder is applied in powder compact forming process.Tool
For body, Fig. 9 is to show the load-deformation curve in the case that metal dust is pure Al (aluminium) and in the case of being aluminium alloy
The chart of figure.It should be noted that Fig. 9 stress-strain curve is the axle that will represent stress semilog expressed in logarithmic
Chart.
As shown in figure 9, in the case where metal dust is pure Al (aluminium), yield stress is point A1Stress be YS1, it is maximum
Stress is point A2Stress be MS1.Therefore, in the case that the metal dust contained in mixed-powder 50 is pure Al (aluminium), by powder
The pressure that mixed-powder 50 is applied in last pressed compact forming process is set as yield stress YS1Above, maximum stress MS1Below.Need
It is noted that the strain on Fig. 9 pure Al load-deformation curve is point A1Region below is represented with curve, but is somebody's turn to do
Region is the stress elastic deformation area proportional relative to the increase of dependent variable.Represent that the region is due to Fig. 9 with curve
For semi-log chart.
In addition, in the case where metal dust is aluminium alloy, yield stress is point B1Stress be YS2, maximum stress is a little
B2Stress be MS2.Therefore, in the case that the metal dust contained in mixed-powder 50 is aluminium alloy, powder compact is shaped
The pressure that mixed-powder 50 is applied in process is set as yield stress YS2Above, maximum stress MS2Below.Need explanation
It is that strain is point B on the load-deformation curve of Fig. 9 aluminium alloy1Following region is point A with above-mentioned strain1Following area
Domain is elastic deformation area similarly.
Stressed processing is applied in powder compact forming process to mixed-powder 50 generally to carry out at normal temperatures.In addition, powder
It is usually 5~60 seconds, preferably 10~40 to apply the stressed time in last pressed compact forming process to mixed-powder 50.In this work
In sequence, the organic matter such as the elastomer of mixed-powder 50 without progress a few houres heat treatment in need, and be by mixed-powder 50
Compress with the physical treatment of the powder compact 60 of formed powder, be therefore, it is possible to make to apply mixed-powder 50 the stressed time
Very short time.
If applying the pressure in preset range to mixed-powder 50 in powder compact forming process, in powder compact
From the powder compact 60 of the formed powder of mixed-powder 50 in the blank part 83 of forming containers 80.The powder compact 60 of powder for example by
Ejection, so as to be discharged from the blank part 83 of powder compact forming containers 80.The powder compact 60 of obtained powder is provided to
Subsequent processing is extrusion manufacturing procedure.
(extrusion manufacturing procedure)
Extrusion manufacturing procedure be with vacuum atmosphere, more than 400 DEG C, 0.1~100s of rate of straining-1Condition to powder
The process that powder compact 60 carries out extrusion processing.
In extrusion manufacturing procedure, the powder compact 60 of powder is heated, and carries out extrusion processing, so as to obtain carbon nanometer
Pipe composite 1.The method for carrying out extruding processing as the powder compact 60 to powder, can use known method, for example
Using after the powder compact 60 of powder is put into the extrusion processing unit (plant) of tubular, to the powder compact of the powder in the container
60 heat and carry out the method for extruding processing.
Referring to the drawings, extrusion manufacturing procedure is illustrated.Figure 10 is the figure of one for showing to extrude manufacturing procedure.Figure 10
In the extrusion processing unit (plant) 90 that shows be that processing is heated and extruded for the powder compact 60 to powder with forming carbon nanometer
The device of pipe composite 1.Extrusion processing unit (plant) 90 has：The apparatus main body 91 of tubular, it is provided with the powder for loading powder
The columned hollow hole part 93 of pressed compact 60；With mould 95, it is arranged on the bottom of apparatus main body 91, discharge extrusion machining object.
In extrusion manufacturing procedure, in the powder compact of the powder to being encased in the hollow hole part 93 of extrusion processing unit (plant) 90
After 60 are heated under vacuum atmosphere, apply reference F2 power, extruded from mould 95 to direction of extrusion M.Need explanation
, atmosphere can replace vacuum atmosphere using non-active gas atmosphere.
The heating of the powder compact 60 of powder is usually more than 400 DEG C with the temperature of the powder compact 60 of powder, is preferably
400~700 DEG C, more preferably 400~660 DEG C, more preferably 400~650 DEG C of mode carries out.If the powder of powder
The temperature of pressed compact 60 then extrudes processing difficulties less than 400 DEG C.In addition, if the temperature of the powder compact 60 of powder is more than 660
DEG C, then worry to generate the carbide (aluminium carbide) of aluminium in carbon nano tube compound material 1.
In addition, the heating of the powder compact 60 of powder with the temperature of the powder compact 60 of powder in the range of said temperature
Time, which is typically 0.3~5 minute, be preferably the mode of 0.5~3 minute is carried out.In this process, the powder compact 60 of powder is not
The organic matter such as elastomer being heat-treated containing a few houres in need, moreover, the carbon nano tube compound material 1 obtained in this process is not yet
With cell columnar structure.Therefore, in this process, the heat time that can make the powder compact 60 of powder is very short time.
Rate of straining during the extrusion processing of the powder compact 60 of the powder of heating is typically 0.1~100s-1, it is preferably
0.3~3s-1.If the carbon nano tube compound material 1 that rate of straining within the range, is obtained has of the present embodiment
The construction and characteristic of carbon nano tube compound material.
Extrusion ratio during extrusion processing is usually more than 4.If extrusion ratio is less than 4, the powder compact 60 of powder is worried
Sintering it is insufficient.Herein, the sectional area of the cross section of the powder compact 60 for being meant that powder of extrusion ratio is relative to conduct
The ratio between sectional area of cross section of carbon nano tube compound material 1 of extruded material.
There is carbon nano tube compound material 1 obtained from being processed via above-mentioned extrusion the CNT with present embodiment to answer
The identical of condensation material 1 is constructed.Therefore, the explanation to carbon nano tube compound material 1 is omitted.
The manufacture method of carbon nano tube compound material of the present embodiment can it is high with short time manufacture conductance and
The few carbon nano tube compound material of the use level of CNT.It should be noted that the conductance of carbon nano tube compound material 1 becomes
High the reasons why is considered as because carbon nano tube compound material 1 does not have cell columnar structure, so need not use bullet during manufacture
Property body, in the absence of residue caused by the gasification because of elastomer.In addition, carbon nano tube compound material 1 can be manufactured with the short time
The reasons why be because, it is not necessary to the gasification operation of elastomer, though comprising powder compact forming process and extrusion manufacturing procedure,
Can be with about 2 minutes manufacture carbon nano tube compound materials 1.
[embodiment]
Hereinafter, using embodiment and comparative example, the present invention will be described in more detail, but the invention is not restricted to these realities
Apply example.
[embodiment 1]
(doped carbon nanometer pipe production process)
＜ pre-treatments ＞
First, diameter about 15nm, the CNT 40 of about 5 μm of average length are prepared.As CNT 40, using advance
CNT 40 is configured to the i.e. so-called Buckie paper of non-woven fabric-like.The thickness of the CNT (Buckie paper) 40 of non-woven fabric-like
It is 0.3mm.Secondly, the CNT 40 of the non-woven fabric-like is impregnated 24 hours in the nitration mixture comprising concentrated nitric acid and the concentrated sulfuric acid.
The impregnation process is the preceding processing of metallic catalyst, amorphous carbon remained as removing in CNT 40 and carried out.
＜ electrolysis processing ＞
Then, using the electrolysis unit 30 shown in Fig. 4, enter to exercise CNT attachment or comprising the iodine as dopant
Electrolysis is handled.Electrolysis unit 30 has：Electrolytic cell 31, it can accumulate the electrolyte 35 containing iodide ion；The Pt anodes of tabular
33, it can load CNT 40；With Pt negative electrodes 34, it can be electrolysed between Pt anodes 33.
First, the NaI aqueous solution 35 as electrolyte is filled in the electrolytic cell 31 of electrolysis unit 30, in electrolytic cell 31
Bottom configuration tabular Pt anodes 33 on mounting include the non-woven fabrics 40 of CNT.The NaI aqueous solution 35 is containing Na+With
I-Electrolyte.
Then, Pt negative electrodes 34 are impregnated in the NaI aqueous solution 35, using the current potential of Pt negative electrodes 34 as the current potential of 0V, Pt anode 33
Potential electrolysis is fixed in the mode for being 0.7V for 0.7V, potential difference.The liquid temperature of the NaI aqueous solution 35 during electrolysis is set as 25
℃.The electrolysis is in order to by the iodide ion I in the NaI aqueous solution 35-It is drawn to Pt anodes 33 and adheres to or be wrapped in Buckie paper
40 CNT and carry out.In addition, electrolytic condition is set to：Buckie paper 40 after electrolysis (after doping) is for carbon nanometer
The mass parts of pipe 100 adhere to the mass parts of iodine 10.
A part for Buckie paper 40 after electrolysis is handled is put into DMF (DMF), applies ultrasound
Ripple vibrates, dissolving Buckie paper 40.Then, when the DMF is gasified, the powder of the CNT after electrolysis processing is obtained.In addition, being directed to
When the Buckie paper 40 of electrolysis before processing has also carried out same processing, the powder for the CNT for being electrolysed before processing has been obtained.
For the powder of these CNTs of electrolysis before and after the processing, Raman spectrum is analyzed.Its result is as shown in figure 5, right
In the CNT after electrolysis processing (after doping), detect non-existent in the CNT of electrolysis before processing (before doping)
111cm-1(I3 -) and 173cm-1(I5 -) peak.It can be seen from Fig. 5 result, the CNT after electrolysis processing (after doping)
In, CNT, which turns into, includes I3 -、I5 -The doped carbon nanometer pipe of the iodine of form.
(powder compact forming process)
First, the Buckie paper 40 after 1 mass parts electrolysis is handled is put into DMF (DMF), is applied
Ultrasonic activation, dissolving Buckie paper 40, so as to obtain doped carbon nanometer pipe.Then, addition purity 99.9%, average grain diameter D50For
50 μm of the mass parts of aluminium powder 100, are mixed in DMF.Then, DMF is gasified, prepare and contain aluminium powder and doped carbon nanometer pipe
Mixed-powder.
Then, mixed-powder is put into the blank part 83 of the powder compact forming containers 80 shown in Fig. 8, at normal temperatures
(20 DEG C) apply pressure 20 seconds to mixed-powder.Bent it should be noted that applying aluminium powder in mixed-powder to mixed-powder
Take more than stress, the pressure below maximum stress.As a result, in the internal shaping powder of blank part 83 of powder compact forming containers 80
Powder compact.
(extrusion manufacturing procedure)
Further, the powder compact of powder is put into the hollow hole part 93 of the extrusion processing unit (plant) 90 shown in Figure 10,
Under vacuum atmosphere, the design temperature for making mould 95 is 500 DEG C, is kept for about 2 minutes, carries out extrusion processing.Extrusion processing is set as
Rate of straining 1s-1.In addition, the extrusion ratio for extruding processing is set as into 4.
After extrusion is machined, carbon nano tube compound material is obtained.Obtained carbon nano tube compound material has：Metal
Base material, it is made up of the polycrystal for being oriented to equidirectional of multiple bar-shaped metal grains；With carbon nanotube conducting path portion, its
It is made up of doped carbon nanometer pipe.The carbon nanotube conducting path portion is present in bar-shaped metal grain in the cross section of metal base
Between crystal boundary a part, and along metal base long side direction exist, so as to form the long side direction in metal base
Conductive conductive path.
In figure 6 and figure 7, indulged after use FIB (focused ion beam method) processing for showing obtained carbon nano tube compound material
Transmission electron microscope (TEM) photo in section.Herein, longitudinal section is the long side direction L along carbon nano tube compound material
Section.Fig. 6 and Fig. 7 are the photos observed with the different visuals field in the longitudinal section of same material.It should be noted that in Fig. 6
In Fig. 7, the region that carbon nanotube conducting path portion 20 is present is represented with reference number C.
It will be appreciated from fig. 6 that carbon nanotube conducting path portion 20 is intermittently deposited between bar-shaped metal grain 11 along long side direction L
.In addition, as shown in Figure 7, carbon nanotube conducting path portion 20 is vertical with its along long side direction L between bar-shaped metal grain 11
Direction (lower section in Fig. 7) exists deviously.
(evaluation)
Doped carbon nanometer pipe amount ＞ in ＜ carbon nano tube compound materials
Using burning-infrared absorption, the doped carbon nanometer pipe amount in obtained carbon nano tube compound material is carried out
Measurement.The carbon nano tube compound material of embodiment 1 contains doped carbon for the mass parts of aluminium 100 of the bar-shaped metal grain 11 of formation
The mass % of nanotube 1.Measurement result is shown in table 1.
[table 1]
The doping ＞ of dopant in ＜ doped carbon nanometer pipes
Using ICP-MS methods, the doping of the dopant in the doped carbon nanometer pipe contained in carbon nano tube compound material is determined
Amount.Doped carbon nanometer pipe in the carbon nano tube compound material of embodiment 1 contains conduct relative to the mass parts of CNT 100
The mass parts of iodine 1.5 of dopant.Measurement result is shown in table 1.It should be noted that as described above, compound as CNT
The raw material of material is the doped carbon nanometer pipe for constituting the Buckie paper 40 after electrolysis processing, is relative to the mass parts of CNT 100
It is attached to the material rich in iodine of the mass parts of iodine 10.Because, it is contemplated that making doping from the Buckie paper 40 after I2 doping
During the powder of CNT, iodine departs from from doped carbon nanometer pipe, so as to adhere to making iodine volume in advance.
＜ conductances ＞
For obtained carbon nano tube compound material, according to JIS C3002, conductance is evaluated.For conductance, keeping
In the thermostat of 20 DEG C (± 0.5 DEG C), using four-terminal method, the ratio resistance of carbon nano tube compound material is measured, according to this than electricity
Resistance calculates conductance.Distance between terminal when measuring ratio resistance is set as 1000mm.It should be noted that conductance is with will be except
Instead of doped carbon nanometer pipe using undoped with CNT beyond, the carbon nanometer that is made with condition similarly to Example 1
Pipe composite is the relative electric conductivity when conductance of comparative example 1 is set as 1.00 to represent.Relative electric conductivity is shown in table
1。
[comparative example 1]
Except replace doped carbon nanometer pipe and use undoped with CNT in addition to, similarly to Example 1, make carbon
Nanometer tube composite materials.For obtained carbon nano tube compound material, evaluated similarly to Example 1.By measurement result
It is shown in table 1.
[embodiment 2 and embodiment 3]
Except changing as shown in table 1 in doped carbon nanometer pipe amount and doped carbon nanometer pipe in carbon nano tube compound material
Beyond the doping of dopant, similarly to Example 1, carbon nano tube compound material is made.Answered for obtained CNT
Condensation material, is evaluated similarly to Example 1.Measurement result is shown in table 1.It should be noted that conductance is with will be except
Instead of doped carbon nanometer pipe using undoped with CNT beyond, received with the carbon made with the same condition of embodiment 2 and 3
Mitron composite is the relative electric conductivity when conductance of comparative example 2 is set as 1.00 to represent.
[comparative example 2]
Except replace doped carbon nanometer pipe and use undoped with CNT in addition to, carbon is made similarly to Example 2
Nanometer tube composite materials.For obtained carbon nano tube compound material, evaluated similarly to Example 1.By measurement result
It is shown in table 1.
[embodiment 4~6]
Except changing as shown in table 1 in doped carbon nanometer pipe amount and doped carbon nanometer pipe in carbon nano tube compound material
Beyond the doping of dopant, similarly to Example 1, carbon nano tube compound material is made.Answered for obtained CNT
Condensation material, is evaluated similarly to Example 1.Measurement result is shown in table 1.It should be noted that conductance use will compare
The relative electric conductivity when conductance of example 2 is set as 1.00 is represented.
[comparative example 3]
In addition to without using doped carbon nanometer pipe, similarly to Example 1, the metal material being only made up of aluminium is made.
For obtained metal material, evaluated similarly to Example 1.Measurement result is shown in table 1.
The result of the relative electric conductivity of embodiment 1~6 is shown in Figure 11.As shown in Figure 11, if in doped carbon nanometer pipe
The doping of dopant (iodine) is in the scope shown in Figure 11 R, i.e. in the range of 0.04~1.6 mass parts, side carbon is received
The relative electric conductivity of mitron composite is uprised.
More than, using embodiment, the present invention is described, but the invention is not restricted to this, can be in master of the invention
Various modifications are carried out in the range of purport.
Carbon nano tube compound material of the present embodiment can for example enter exercise as the wire rod of automobile wiring harness
With.
Claims (8)
1. a kind of carbon nano tube compound material, it is characterised in that
Including：
Metal base, it is made up of polycrystal, and multiple bar-shaped metal grains is oriented to equidirectional in the polycrystal；And
Carbon nanotube conducting path portion, it is made up of the doped carbon nanometer pipe with dopant, in the transversal of the metal base
It is present in a part for the crystal boundary between the bar-shaped metal grain in face, and is deposited along the long side direction of the metal base
So as to be formed in the conductive conductive path of the long side direction of the metal base.
2. carbon nano tube compound material according to claim 1, it is characterised in that
The dopant is selected from the group being made up of the material containing halogens, the material of alkali metal containing and metal oxide
More than one dopants.
3. carbon nano tube compound material according to claim 2, it is characterised in that
The material containing halogens be selected from the group being made up of fluorine, chlorine, bromine and iodine more than one elements, comprising institute
State the ion, the molecule comprising more than one elements or its compound of more than one elements.
4. carbon nano tube compound material according to claim 2, it is characterised in that
The material of the alkali metal containing is more than one elements selected from the group being made up of lithium, sodium, potassium, rubidium and caesium, included
The ion of more than one elements, the molecule comprising more than one elements or its compound.
5. carbon nano tube compound material according to claim 2, it is characterised in that
The metal oxide is from the group being made up of iron oxide, cupric oxide, titanium oxide, zinc oxide, molybdenum oxide and calcium oxide
More than one oxides selected.
6. according to carbon nano tube compound material according to any one of claims 1 to 5, it is characterised in that
The dopant of the doped carbon nanometer pipe is constituted relative to the mass parts of CNT 100, there are 0.04~1.6 mass parts.
7. according to carbon nano tube compound material according to any one of claims 1 to 6, it is characterised in that
Constitute the dopant attachment of the doped carbon nanometer pipe or be contained in CNT.
8. according to carbon nano tube compound material according to any one of claims 1 to 7, it is characterised in that
Relative to the mass parts of metal base 100, contain the mass parts of carbon nanotube conducting path portion 0.1~1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011090133A1 (en) * | 2010-01-20 | 2011-07-28 | 古河電気工業株式会社 | Composite electric cable and process for producing same |
| WO2015156038A1 (en) * | 2014-04-08 | 2015-10-15 | 矢崎総業株式会社 | Carbon nanotube composite material and process for producing same |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100790216B1 (en) * | 2006-10-17 | 2008-01-02 | 삼성전자주식회사 | A transparent cnt electrode using conductive dispersant and preparation method thereof |
| CN102224596B (en) * | 2008-06-09 | 2015-06-17 | 三星电子株式会社 | Improved cnt/topcoat processes for making a transplant conductor |
| WO2011033377A2 (en) * | 2009-09-17 | 2011-03-24 | Vive Nano, Inc. | Multifunctional nanocomposites |
| US20140084219A1 (en) * | 2011-02-28 | 2014-03-27 | William Marsh Rice University | Doped multiwalled carbon nanotube fibers and methods of making the same |
| US9263524B2 (en) * | 2011-04-05 | 2016-02-16 | The Board Of Trustees Of The Leland Stanford Junior University | Semiconductor materials, apparatuses and methods |
| US8808792B2 (en) | 2012-01-17 | 2014-08-19 | Northrop Grumman Systems Corporation | Carbon nanotube conductor with enhanced electrical conductivity |
| JP2014047093A (en) * | 2012-08-30 | 2014-03-17 | Toyota Motor Corp | Electroconductive material and method for producing the same |
| US9455439B2 (en) * | 2012-11-21 | 2016-09-27 | Ut-Battelle, Llc | Nitrogen—sulfur—carbon nanocomposites and their application as cathode materials in lithium—sulfur batteries |
| US9896340B2 (en) * | 2013-07-18 | 2018-02-20 | William Marsh Rice University | Rebar hybrid materials and methods of making the same |
| JP6247771B2 (en) * | 2014-09-08 | 2017-12-13 | 富士フイルム株式会社 | Thermoelectric conversion element and thermoelectric conversion module |
-
2015
- 2015-11-24 JP JP2015228668A patent/JP6390027B2/en active Active
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011090133A1 (en) * | 2010-01-20 | 2011-07-28 | 古河電気工業株式会社 | Composite electric cable and process for producing same |
| WO2015156038A1 (en) * | 2014-04-08 | 2015-10-15 | 矢崎総業株式会社 | Carbon nanotube composite material and process for producing same |
Non-Patent Citations (1)
| Title |
|---|
| 石国娴 徐学诚: "卤素掺杂对多壁碳纳米管导电性能的影响", 《华东师范大学学报（自然科学版）》 * |
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| CN107039103B (en) | 2019-07-16 |
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